Dye stuffs comprising derivatives of anthraquinone for dyeing live human hair and use thereof



United States Patent US. Cl. 810.1 23 Claims ABSTRACT OF THE DISCLOSURE This invention relates to processes and compositions for dyeing human hair with dyestuffs of the formulas:

(1) 0 NHZ mNHZ X n X in which one X is -NHZ and the others are hydrogen and NH-Z is in which R and R are lower alkyl or together with the adjacent nitrogen represent a heterocyclic radical; or N,N- dirnethyl-p-phenylenediamine;

n is 2 or 3, and R, R together with the adjacent nitrogen are as previously defined; and

(3) 0 NH(CHz)nNZ if R n and R are as defined for Formula 1, NZ is a heterocyclic radical, and A is an anion.

This application is a continuation of application of Ser. No. 319,635 filed on Oct. 24, 1963, which is now abandoned.

This invention relates to dye stuffs and to their use in dyeing live human hair with derivatives of anthraquinone.

There are four general classes of compounds described in this invention. The first class has a substitution in the No. 1 position and a second substitution in other positions on the nucleus. The second class has a hydroxy group in the No. 4 position and a substitution in the No. l position on the nucleus. The third class has a single substitution in the No. 2 position on the nucleus. The fourth class has a single substitution in the No. 1 position on the nucleus. These classes will be described consecutively.

Accordingly to the first class of the present invention, a process for dyeing of hair and like keratinous materials comprises applying thereto one or more dyestuffs of the formula:

X 0 NH-Z NHZ l n 1 X 0 X in which one X is an NHZ radical and the other two are hydrogen and Z represents a group of the formula in which R and R are the same or different and represent lower alkyl radicals or together with the adjacent nitrogen represent a saturated mononuclear heterocyclic radical and n is an integer from 2 to 6, or quaternary ammonium salts of such dyestuffs.

The dyestuffs of Formula 1 in which R and R together with the adjacent nitrogen represent a saturated mononuclear heterocyclic residue and their quaternary ammonium salts are new compounds and as such within the'scope of the invention.

Especially valuable dyestuffs of Formula 1 are those in which n is 2, 3 or 6 and R and R are each a lower alkyl radical or together with the adjacent nitrogen represent a piperidino or morpholino radical. Especially valuable quaternary ammonium salts of such dyestuffs are the bis(methyl methosulphates) and the bis(benzyl chlorides).

The dyestuffs of Formula 1 and the quaternary ammonium salts dye hair excellently at room temperature, and, because they contain two tertiary or quaternary nitrogen atoms, they possess a high affinity for the hair over the wide pH range of 3 to 10, and especially 4.5 to 9.5, depending upon whether their tertiary or quaternary derivatives are employed.

Moreover, the aforesaid dyestuffs are very soluble in water, because of the number of basic groupings they contain, and it is thus possible to obtain aqueous dye solutions Whose concentration may exceed 10%.

The dyestuffs have the further advantage that the dyeing effects obtained with them are relatively fast to sunlight. Thus, their fastness is approximately equal to that of standard 4 on the range established by the Association for the Determination of the Fastness of Dyeing Effects and Textile Prints (see Code de Solidite, pub-- lished by the Groupement dEtudes Continental Europeen, 2nd Edition (1958), p. 31), when this standard and the dyeings obtained in accordance with this invention are simultaneously. exposed to sunlight under similar conditions. The aforesaid range of standards extends from 1 to 8, 8 representing the greatest degree of fastness.

It is possible by appropriately choosing the positions of the two amino groupings of the anthraquinone molecule to obtain dyes of very varied shades ranging from red to blue and blue-green. Consequently, natural shades very popular with consumers can readily be obtained by using mixtures of dyes.

Some of the aforesaid dyestuffs, especially those containing morpholine or piperidino residues, are particularly suitable, as they give off no unpleasant odor when used in hair dyeing.

The present invention provides, as a further feature, hair dyeing compositions containing one or more dyestuffs of Formula 1 or quaternary ammonium salts thereof in an aqueous solution having a pH between 3 and 10, preferably 4.5 and 9.5.

4 tained is evaporated to dryness and the residue dissolved in benzene. The benzene solution is then washed with a 10% sodium hydroxide solution and dried and evaporated to remove solvent. The dyestufi is thus obtained in a yield of 90%. When recrystallized from hexane, it

These compositions may comprise only dyestuffis of 5 melts at 157 C.

Formula 1 or quaternary ammonium salts thereof, in Analysis.Calculated: C percent, 67.24; H percent,

which case the color obtained ranges from red to blue- 6.89; N percent, 12.06. Found: C percent, 67.15-66.93;

green; but it is also possible to mix such dyes with other H percent, 7.00-6.91; N percent, 11.87-11.77.

dyes conventionally employed in hair dyeing.

These compositions may be very readily Prepared by w Examp 1e g; b1?(methyimorpholmlumethylammo) qumone]d1methosulphate CllSSlV1Ilg in water one or more dyestuffs of Formula 1 or quaternary ammonium salts thereof optionally mixed E H with other dyes and adjusting the pH to the desired value 0 NH-CHz-CHr-N within the range 3 to 10. There may be incorporated in H l these dyeing solutions various products usually employed in the cosmetics field, such as wetting and dispersing 2(S0rGHr) agents, emollients, and perfumes.

The compositions of the invention may be applied to I the hair in the usual manner, preferably at room temper- 0 NH-CIL-Clih-N ature. The concentration of the dye may vary within wide HrCL/II limits, depending upon the depth of dyeing aimed at.

The dyestuffs of Formula 1 may be obtained from This product is readily obtained from the correspondquinizarin or 1,5 or 1,8-dichloroanthraquinone by the acing base by the action of methylsulphate, using toluene as tion of a diamine of the formula: solvent, under reflux in the usual way. On recrystallization from methanol, it melts with decomposition at 240- 245 c. NHz-(CHzh-N Analysis.-Calculated: N percent, 7.82. Found: N per- (2) cent 7.77-7.60.

in which n, R and R' are as hereinbefore defined. Examp 1e of PIS (fl'morpholmo' y am1no)anthraqurnone The tertiary anuno anthraqulnone derivatives thus obtained may be quaternized very readily in the usual man- CHFCH' ner with a quaternizing agent such as methylsulphate or o NH-cm-om-N 0 an alkyl or benzyl halide, in the presence or absence of H GHrCQ, an appropriate solvent such as toluene. A

The following non-limiting examples illustrate the preparation of the new dyestuffs of Formula 1 and their quaternary ammonium salts (in Examples I to X) and l the use of dyestuffs of Formula 1 in the dyeing of hair. 40 0 NCH2--CH2NH 0 CH2CH1 Example gf gg i h g gi g This product is obtained by the action of a slight excess of fi-aminoethylmorpholine on 1,5-dichloroanthra- CHPCH, quinone, using isobutanol as solvent, under reflux for 6 M hours. After cooling, the crude product precipitates, and 1? NH Cm N is purified by repeated recrystallization from alcohol. 3112-9112 M.P.=203 C. \l Analysis.-Calculated: C percent, 67.24; H percent, 6.89; N percent, 12.06. Found: C percent, 67.12-67.23; \I/ I (311F011, H percent, 6.75-6.78; N percent, 11.85-11.80.

NH CH1 OH2 N Example IV.--[1,5-bis(methylmorpholiniumethyl- CHz-OHg amino)anthraquinone]dimethosulphate CHr-CH: 0 NH-CHPCHIN/ 0 ll l CHI CHr-CH O 2(SOlCH3 CHr-CH Y O\ /N\\OH2CH:NH O

GET-CH2 CH:

A mixture of 0.06 g. mol of quinizarin, 0.06 g. atom of zinc and 0.2 g. mol of B-aminoethylmorpholine in 100 cc. of isobutanol is heated under reflux for 3 hours.

After oxidation of the intermediate leuco derivative This product is obtained from the corresponding base by the action of methylsulphate in toluene. It melts with decomposition at 250 C.

Analysis.-Calculated: N percent, 7.54. Found: N perthus formed and filtration of the zinc, the mixture obcent, 7.56-7.65.

6 Example V.-Preparation of 1,4-bis(w-morpholinohexyl- Example IX.-Preparation of 1,4-bis -piperidinopropylamino) anthraquinone amino) anthraquinone CHr-CH: CHz-CHI o NH- oHm-N o o NH-CH;CHa-OH;N CH: II I 5 II I CHa-CH: CH2CH2 uni-cg, I era-cg:

o NH-(OHzh-N o 10 o NH-CHz-CHrCHr-N on,

CHa-CH: CHz-C; A mixture of quinizarin, zinc powder and aminohexyl- A mixture of quinizarin, zinc powder, and -amino-promorpholine in isobutanol is refluxed with stirring, in the pylpiperidine in isobutanol is refluxed with stirring, in the same way as in Example I, for 4 hours. After working up same way as in Example I, for 10 hours. After working as in Example I, the desired product is obtained in a up as in Example I, the desired product is obtained in a yield of 50%. After recrystallization from heptane, it yield of about 50%. When recrystallized from petroleum melts at 71 C. ether and from alcohol, it melts at 123 C.

Analysis.Calculated: C percent, 70.83; H percent, Analysis.-Calculated: C percent, 73.77; H percent, 8.33; N percent, 9.72. Found: C percent, 70.87-70.98; H 8.19. Found: C percent, 73.83-73.82; H percent, 8.18- percent, 7.97-8.27; N percent, 9.57-9.50. 8.23.

Example VI.Preparation of [1,4-bis (methylmorpholiniumaminohexyl anthraquinone] dimethosulphate C Hr-C H: 0 Nil-(0H2) |N/ CHPCHQ H i O N HC Hr- O Hz-CHz-N CH2 0 NH C H2) oN O H I HKQCHPCQI 0 NH-om-om-om-N om This product is obtained from the above-described cor- CHPCH responding tertiary base by quaternization under reflux Y CHz-CgHs with methylsulphate in toluene. It is very hygroscopic and is therefore immediately employed without purification. Thls E obtamed m the conespondfng base by the action of benzyl chlorlde under reflux, using tolu- Example -P p of (fip one as solvent. It melts with decomposition at 165-170 0.

Example X.Preparation of [l,4-bis(benzylpiperidiniumpropylamino)anthraquinone] dichloride ylamino)anthraquinone 40 orig-0H, CHHm, Example XI 0 NmCHPCHPNH 0 NIFOHPCHPN The following mixture is prepared: I I (311F041, 1,4-bis (p-morpholinoethyla-mino) anthraquinone4.6 g.

Acetic acid to pH 4.8 Water to 100 cc.

\/ This solution is applied to 95% white hair and left in contact therewith for 10 to 15 minutes at room temperature. The hair is then abundantly rinsed with water and This product is obtained in the same way as the proddfled- A blue-green colofatlon 1S Obtalnednet of Example III from 1,8-dichloroanthraquinone by Example XII reaction with aminoethylmorpholine. When recrystallized from hexane, it melts at 170-171 C. The following mixture is prepared:

Analysis.-Calculated: C percent, 67.24; H percent, I 6.89; N percent, 12.06. Found: C percent, 67.27-67.03; H ifiggfi figfigf i g Percent 116-696; N Percent 1237-1225 C -C fatty alcohol (from copra) condensed with 10 Example VIIL-Preparation of [1,8-bis(methylmorphomolecules of ethylene oxide10 g.

liniumethylamino)anthraquinone]dimethosulphate Na CO to pH 7 CHr-OH: CHa-CH:

This product is obtained in the usual way from the cOr- Water to 100 cc. responding base by the action of methylsulphate. When This solution, when applied under the same conditions recrystallized from alcohol, it melts at ZOO-201 C. with as in the foregoing example, gives an intense blue shade decomposition. to grey hair.

7 Example XIII The following mixture is prepared:

[ 1,8-bis (methylmorpholiniumethylamino) anthraquinone] dimethosulphate-0.5 g.

Octylphenol condensed with to 11 molecules of ethylene oxide-2.5 g. Na CO to pH 9.5 Water to 100 cc.

When applied to grey hair and left in contact therewith for 10 to minutes at room temperature, this solution gives the hair after rinsing a violet-tinged coloration.

Example XIV The following mixture is prepared:

[ 1,8-bis(trimethylammoniumpropylamino)anthraquinone]dirnethosulphate-4 g.

% ammonium solution to pH 9 Water to 100 cc.

Under the same conditions as in Example XIII, hair with a violet mauve coloration is obtained.

Example XV The following mixture is prepared:

[ 1,5 -bis (trimethylammoniumpropylamino) anthraquinone] dimethosulphatel g.

Octylphenol condensed with 10 to 11 molecules of ethylene oxide-2.5 g.

Water to 100 cc.

Under the same conditions as in Example XIII, a violet pink coloration is obtained.

Example XVI The following mixture is prepared:

[1,S-bis(methylmorpholiniumethylamino) anthraquinone] dimethosulphate-4 g. Na CO to pH 9 Water to 100 cc.

Under the same conditions of application as in Example XV, a similar tint is obtained.

Example XVII The following mixture is prepared:

1,S-bis(p-morpholinoethylamino) anthraquinone-4 g. Lactic acid to pH 4.8 Water to 100 cc.

Under the same conditions of application as in the above examples, hair with a pink shade is obtained.

Example XVIII The following mixture is prepared:

l,4-bis ('ydimethylaminopropylamino) anthraquinone- Lactic acid to pH 6 Water to 100 cc.

When applied to hair under the same conditions as in the above examples, this solution gives the hair a bluegreen coloration.

Example XDC The following mixture is prepared:

[ 1 ,4-bis (trimethyl ammoniumethyl amino) anthraquinone] dimethosulphate2 g.

Octylphenol condensed with 10 to II molecules of ethylene oxide2 g.

Na2CO3 to 8 Water to 100 cc.

When applied to white hair under the same conditions as in the above examples, this solution gives the hair a marked blue coloration.

Example XX The following mixture is prepared:

1,8-bis(dimethylaminopropylamino)anthraquinone-l g. Lactic acid to pH 3.5 Water to cc.

After application to white hair under the same conditions as in the above examples, a fine Parma Violet coloration is obtained.

Example XXI The following mixture is prepared:

1,4-bis('y-piperidinopropylamino) anthraquinone-3 g. Lactic acid to pH 4.8 Water to 100 cc.

When applied as in the above examples, this solution gives hair a pale blue shade.

Example XXII The following mixture is prepared:

[1,4 bis (benzylpiperidiniumpropylamino)anthraquinone] dichloride-4.5 g. Na CO to pH 9 Water to 100 cc.

This solution is applied to hair for 15 minutes in accordance with the above examples and colors it azure blue.

Example XXIII The following mixture is prepared:

This solution is applied to 100% white hair, and left in contact therewith for 10 minutes at room temperature. After rinsing, shampooing and drying, the hair is a fine light-brown color lightly tinged with pink.

Example XXIV The following mixture is prepared:

4-nitro-m-phenylenediamine-0.3 g. 1,4 bis('y dirnethylaminopropylamino)anthraquinone--l g. 1,8 bis(7 dimethylaminopropylamino)anthraquinone-15 g.

4-nitro-o-phenylenediamine0.3 g. 4% citric acid solution to pH 5 Water to 100 cc.

Under the same conditions as in the above examples, 90% white hair is dyed a copper-tinged light-brown color.

Example XXV-Preparation of 1.4-(p-dimethylaminophenyl) amine anthraquinone This product is obtained on heating for 12 hours at 90 C. a mixture of leucoquinizarine, and excess of N,N-dimethyl-p-phenylenediamine, boric acid and water. At the end of the reaction, and before the passage of a current of air in order to oxidize the formed leuco derivative, the product is dried, then by washing the crude product thus obtained with alcohol, the excess N,N-dimethyl-p-phenylene diamine is eliminated. The crude product thus obtained is purified and recrystallized in chlorobenzene melting at 275 C.

Analysis.-Calculated: C percent, 75.62; H percent, 5.88; N percent, 11.74. Found: C percent, 75.40-75.36; H percent, 6.04-5.98; N percent, 11.44-11.36.

Example XXVL-Preparation of bis-methyl[l,4-p-trimethylanalinium)amino anthraquinone] sulphate This product is obtained starting with 1,4(p-dimethylaminophenyl)amino anthraquinone by reaction with methyl sulphate for 1 hour at 80 C. in solution in nitrobenzene. The corresponding quaternary is precipitated and can be isolated by drying. The product obtained decomposes at 286-288 C.

Example XXVII.Preparation of 1.5-(p-dimethylaminophenyD-amino anthraquinone A mixture of 28.5 g. of 1,5-dichloroanthraquinone and 110 g. of N,N-dimethyl-p-phenylene-diamine are heated for hours at 100 C. They are cooled to 50 C. and dried. The crude product obtained is purified by washing with boiling water, and recrystallized in a chloroform-benzene mixture.

Example XXVIII.Preparation of bis-methyl-[1,5-(ptrimethylaniline)-amino anthraquinone] sulphate This product is obtained by reacting 1,5-(p-dimethylaminophenyl) amino anthraquinone with methyl sulfate for 1 hour at refiuxtemperature in a toluene solution. The corresponding quaternary is dried.

Example XXIX.Preparation of diamino-[l-p-dimethylaminophenyl) -4- (B-morpholino-ethyl) ]-anthraquinone A solution of 24.2 g. of leucoquinizarine and 17.7 g. of N,N-dimethyl-p-phenylenediamine is heated for 4 hours at 100 C. in 200 cc. of isobutanol. In the reaction medium, 24 g. of PhD, and 14 g. of B-aminoethylmorpholine are added, and the temperature is maintained at 100 C. for 2 hours. It is filtered while boiling. After cooling the filtrate, the crude product is dried, which, after recrystallization in dioxane, melts at 226 C.

Example XXX-Preparation of bis-methyl [l-p-trimethylaniline)-4 (p aminoethylrnorpholinium) amino anthraquinone] sulphate This product is obtained by quaternization of liaminol-p-dirnethylamino-phenyl) -4-B-morpholinoethyl)] anthraquinone, with the help of methyl sulphate, in a chloroform solution.

Example XXXI The following mixture is prepared:

Bis-methyl [1,4-(p-trimethylaniline) amino anthraquinone] su1phate-2 g. Sodium carbonate solution, in a quantity sufiicient for pH 7.5 Water to make 100 cc.

This solution is applied to white hair, left in contact therewith for 10 to 15 minutes at room temperature, then rinsed amply with water and dried. A green coloration is thus obtained.

Example XXXII The following mixture is prepared:

Bis-methyl [1,5 p trimethylani1ine)amino anthraquinone] sulphate2.5 g.

Sodium carbonate solution, in a quantity for a pH 9.0

Water to make up to cc.

This solution is applied to 95% white hair, left in contact for to minutes at room temperature, then rinsed amply with water, and dried. A blue-green coloration is thus obtained.

This invention is based on the discovery that the dyestuff of the formula:

in which n is from 2 to 6 and R and R' are the same or different and each represents a lower alkyl group, for example, methyl or ethyl, or together with the adjacent nitrogen atom represent a saturated mononuclear heterocyclic radical, especially a morpholino or piperidino radical, and their acid addition and quaternary ammonium salts, have high aflinity for keratinic fibres over a very wide pH range. The invention accordingly provides compositions for the dyeing of hair comprising a dyestutf of Formula 3 or an acid addition or quaternary ammonium salt thereof.

Of the dyestuffs of Formula 3 those in which R and R together with the adjacent nitrogen represent a saturated mononuclear heterocyclic radical are novel per se and as such within the scope of the invention.

When the tertiary amino group in a dyestutr' of Formula 3 is quaternized, it has preferably the following formula:

in which n, R and R are as hereinbefore defined, R" represents a lower alkyl radical especially methyl, and A represents an anion such as a halogen or, especially, a methosulphate ion.

By way of example of dyestuffs of Formula 3 there may be mentioned the following substances: l-(B-diethylaminoethylamino)-4-hydroxyanthraquinone; 1 ('y diethylaminopropylamino) 4 hydroxyanthraquinone; l-(fl-morpholinoethylamino) 4 hydroxyanthraquinone; 1-(7- piperidinopropylamino) 4 hydroxyanthraquinone, and their acid addition and quaternary ammonium salts.

The dyestufls of Formula 3 have the advantage that they are highly water-soluble over a very wide pH interval, e.g. from 3 to 9, and that they have solubilities reaching about 8%. In addition, they have great aflinity for hair and are very resistant to light. They withstand perfectly the presence of ingredients ordinarily incorporated in dyeing solutions, and such ingredients, especially wetting agents, may be added to the compositions of the invention.

It has also surprisingly been found that dyeing solutions which contain only compounds possessing morpholino or piperidino radicals do not have an unpleasant odor, unlike dyeing solutions containing other anthraquinone dyestuffs of similar formula.

The dyes of Formula 3 also have the advantage that they can be mixed without difliculty with other dyestuffs generally employed in hair dyeing, for example nitro derivatives of the benzene series and other anthraquinone dyestulfs.

The compositions of the invention are readily prepared by simple dissolution in water of one or more of the dyestuffs of Formula 3, in the presence or absence of other dyestuffs, and, where necessary or desirable, introducing into the solution other ingredients generally employed in such compositions such as emollients, perfumes and especially wetting agents. The dyestuff concentration may vary within wide limits and its precise value will depend upon the result desired.

Hair-dyeing with the compositions of the invention is carried out in the usual way by applying the dye solution, preferably at normal temperature, to the hair until it is dyed.

The compounds of Formula 3 may be prepared from 1,4-dihydroxyanthraquinone, also known as quinizarine, by the action of an N,N-dialkylalkylenediamine of the formula:

in which n, R and R are as hereinbefore defined.

The quaternization of the tertiary amino compounds thus obtained is carried out in the usual way by reaction with a quaternizing agent, such as methyl sulphate or an alkyl halide, in the presence or absence of an appropriate solvent.

The following examples illustrate the invention.

Example XXXIV Example XXXV (4 hydroxyanthraquinonyl 1 aminoethyDmethylmorpholinium methosulphate is readily obtained from the base described in Example XXXIV by the action of methyl sulphate, using toluene as solvent and refluxing the mixture in the usual way. The product obtained melts with decomposition between 200 and 205 C. Analysis shows a nitrogen content of 5.73%, compared with a calculated content of 5.75%.

Example XXXVI 1 ('y piperidinopropyl)amino 4 hydroxyanthraquinone is obtained by refluxing for seven hours with stirring a mixture of 0.15 g./mol. of quinizarine and 0.15 g./mol. of aminopropylpiperidine in 200 cc. of toluene. After evaporation of the solvent, the product is recrystallized a number of times from hexane and then from alcohol, and then melts at about C. and analyses as follows:

Calculated: C percent, 72.53; H percent, 6.59; N percent, 7.69. Found: C percent, 72.43-72.35; H percent, 6.72-6.83; N percent, 7.81-8.01.

Example XXXV II For the preparation of (4-hydroxyanthraquinonyl-1- aminopropyl)-methylpiperidinium methosulphate, methyl sulphate is reacted with the corresponding base described in Example XXXVI using benzene as solvent with refluxing in the usual way. The product obtained melts with decomposition at a temperature of -163 C.

Example XXXVIII The following mixture is prepared:

(4 hydroxyanthraquinonyl l aminoethyl) methylmorpholinium methosulphate-5 g.

Fatty alcohol C -C (from copra) condensed with 10 molecules of ethylene oxide--l0 g.

Water to 100 cc.

13 This solution is applied to grey hair and left in contact therewith for to minutes at ambient temperature. The hair is then copiously rinsed with water and dried. It is dyed an intense violet.

Example XXXIX The following mixture is prepared:

(4 hydroxyanthraquinonyl 1 aminoethyl)methyl morpholinium methosulphate1 g.

Lactic acid to pH 3 Water to 100 cc.

By applying this solution under the conditions indicated in the preceding example, a coloration of comparable shade, but of lower intensity, is obtained.

Example XL The following mixture is prepared:

(4 hydroxyanthraquinonyl l aminopropyl)trimethylammonium methosulphate2 g.

Octylphenol condensed with 10 molecules of ethylene oxide l.3 g.

% ammonia to pH 9 Water to 1100 cc.

Under the same conditions of application as in Example XXXVIII, hair containing 90% of white hairs acquires a violet coloration comparable to that obtained in Examples XXXVIII and XXXIX.

Example XLI The following mixture is prepared:

1 dimethylaminopropylamino) 4 hydroxyanthraquinone0.5 g.

Lactic acid to pH 3.5

Water to 100 cc.

This composition dyes hair a violet color comparable with that obtained in Examples XXXVIII to XL when used as described in Example XXXVIII.

Example XLII The following mixture is prepared:

Example XLIII The following mixture is prepared:

(1,4 anthraquinonylaminoethyl) methylmorpholinium bis-methosulphate1.3 g.

(4 hydroxyanthraquinonyl l aminopropyl)methy1- piperidinium methosulphate'0.9 g.

Na CO to pH 7 Water to 100 cc.

When this solution is applied to hair containing 95% of white hairs, under the conditions described in Example XXXVIII, a uniform grey color is obtained.

The new dyestuffs of the invention have the formula:

II R NI-I(CH2),.N/

in which n is from 2 to 6 and R and R each represents a lower alkyl group, or together with the adjacent nitrogen represents a saturated mononuclear heterocyclic radical, and their acid addition and quaternary ammonium salts. In this formula, R and R may be identical or different, and may be, for example, methyl, ethyl or propyl groups, or R and R, together with the adjacent nitrogen, may represent morpholino or piperidino radicals. It is preferred that R and R represent ethyl radicals or, together with the adjacent nitrogen, represent a morpholino radical, and n is 2 or 3.

When the tertiary amino group in Formula 4 is quaternized, the group attached to the anthraquinone nucleus has preferably the following formula:

in which n, R and R are as hereinbefore defined, R" represents a lower alkyl radical, especially methyl, and A" represents an anion, such as a halide or especially a methosulphate ion.

Of the anthraquinone derivatives falling within the scope of the present invention, there may be mentioned, inter alia, the following compounds: Z-(fl-diethylaminoethylamino)anthraquinone; 2 ('y diethylaminopropylamino)anthraquinone; and 2 ([3 morpholinoethylamino)anthraquinone; and their acid addition and quaternary ammonium salts.

It has been discovered that the dyestuffs of Formula 4 and their quaternary ammonium derivatives are very suitable as dyestuffs for dyeing hair, especially at ordinary temperatures. These dyestuffs have, owing to the presence of the tertiary or quaternary amino function, high affinity for hair over a very wide pH range, e.g. of 4.5 to 9, depending upon whether the tertiary or quaternary deriva tives are employed while, in addition, they possess good solubility in water.

The dyeings obtained with these dyestuffs have, the additional advantage of being resistant to sunlight. Finally, the dyestuffs are fully compatible with the adjuvants gen erally present in dyeing solutions.

The dyeings obtained on hair with the dyestuffs of the invention are generally yellow or golden-yellow. This is a considerable advantage because mixtures of the dyestuffs of Formula 4 with the red to blue-green dyestuffs, described in this application, can be used to obtain an interesting range of natural shades.

The invention includes within its scope compositions for dyeing hair which comprise a dyestuff of Formula 4 or acid addition or quaternary ammonium salt thereof. The compositions are generally in the form of aqueous solutions of pH 4.5 to 9 which are very easily prepared by simple dissolution in water of one or more of the new dyestuffs, with or without other dyestuffs. The solutions may also contain, where necessary, the adjuvants generally employed in compositions for dyeing hair, e.g. emollients, and perfumes, and especially wetting agents. The dyestuffs concentration in the dyeing solutions may vary within wide limits and the precise concentration chosen depends upon the result aimed at.

Hair dyeing with the new compositions is carried out in the usual manner by applying them to the hair for an appropriate time, preferably at normal temperature.

The new dyestuffs may be prepared by reacting, for example, B-chloro (or B-bromo)anthraquinone with an alkylenediamine of the formula R Hz 2)nN in which n, R and R are as hereinbefore defined, in the presence of pyridine. The quaternization of the tertiary anthraquinone derivatives thus obtained can be very simply carried out by reacting a quaternizing agent, such 15 as methyl sulphate or an alkyl halide, with the anthraquinone derivative containing the tertiary amino group, in the presence or absence of an appropriate solvent.

The following examples illustrate, on the one hand, the preparation of the new dyestuffs and, on the other, the use of these dyestuffs in hair dyeing.

Example XLIV-Preparation of 2-(B-diethylamin0ethy1) aminoanthraquinone A mixture of ,B-chloroanthraquinone (0.1 g. mol.) and N,N-diethylethylenediamine (0.4 g. mol.) in 50 cc. of pyridine is heated for 8 hours at 100-104 C. After cooling and evaporation of the excess pyridine, the crude product obtained is recrystallized from hexane. The desired product is thus obtained and melts at 122 C.

Analysis.-Calculated: C percent, 74.51; H percent, 6.84; N percent, 8.70. Found: C percent, 74.5-74.33; H percent, 6.61-6.72; N percent, 8.68-8.74.

Example XLV.Preparation of (Z-anthraquinonylaminoethyl)diethylmethylammonium methosulphate The tertiary amino dyestuff described in Example XLIV is reacted with methyl sulphate in the presence of benzene under reflux. After cooling, the desired quaternary ammonium salt precipitates as a yellow powder. It melts with decomposition at a temperature of 194- 196 C.

Analysis.-Calculated: N percent, 6.25. Found: N percent 6.10-6.10.

Example XLV-I.Preparation of Z-(y-dimethylaminO- propyl) aminoanthraquinone By proceeding as in Example XLIV, but using 'y-diethylaminopropylamine, the desired product is obtained and when purified by chromatography through alumina in the usual way, melts at 122 C.

Analysis-Calculated: C percent, 75.00; H percent, 7.14; N percent, 8.33. Found: C percent, 75.05-75.29; H percent, 7.37-7.06; N percent, 8.70-8.39.

Example XLVIL-Preparation of (Z-anthraquinonylaminopropyl)-diethylrnethylammonium methosulphate Methyl sulphate is reacted in the usual way in the cold with the corresponding tertiary base, described in Example XLVI, using benzene as solvent. The product thus obtained melts with decomposition at 128-130 C.

Example XLVIII.Preparation of Z-(fl-morpholinoethyl) aminoanthraquinone By proceeding as in Example XLIV, but using a mixture of fi-chloroanthraquinone and N-aminoethylrnorpholine, there is obtained, after purification of the crude product by chromatography through alumina, the desired product, which melts at 189 C.

Analysis.-Calculated: C percent, 71.43; H percent, 5.95; N percent, 8.33. Found: C percent, 71.39-71.30; H percent, 6.11-6.04; N percent, 8.22-8.02.

Example XLIX.-Preparation of (2-anthraquinonylaminoethyl)-methylmorpholinium methosulphate This product is obtained from the tertiary amino dyestutf described in Example XLVIII, dissolved in chlorobenzene, by the action of methyl sulphate at an elevated temperature. After purification by recrystallization from hexane, the desired product is obtained, M.P. 228230 C. (dec.).

Analysis.Calculated: N percent, 6.06. Found: N percent, 5.90-5.87.

Example L The following mixture is prepared:

(Z-anthraquinonylaminoethyl)-methylmorpholinium methosulphate1 g.

Octylphenol condensed with 10 molecules of ethylene oxide0.9 g.

16 Na CO t0 7 Water to cc.

This solution is applied to blond hair and left in contact therewith for 10 to 15 minutes at ambient temperature, and the hair is then abundantly rinsed with water and dried. An intense golden tint is thus obtained. This solution, when applied in the same way to white hair, colors it a light gold-blond.

Example LI The following mixture is prepared:

(2 anthraquinonylaminoethyl)diethylmethylammonium methosulphate-l g.

Na CO to 7 Water to 100 cc.

This solution, when applied to white hair, as in the precedlng example, gives it a fine gold-blond color.

Example LII The following mixture is prepared:

(2 anthraquinonylaminoethyl) methylmorpholinium methosulphate1 g.

(1,4 anthraquinonylaminoethyl) methylmorpholinium bis-methosulphate0.5 g.

(1,5 anthraquinonylaminoethyl) methylmorpholinium bis-methosulphate'0.5 g.

Water to 100 cc.

By. applying this solution to 100% white hair under the conditions described in Example L, a gold-chestnut color is obtained.

Certain anthraquinone compositions have been proposed for dyeing hair. These have a disadvantage in that their alkaline aqueous solution on standing produces a disagreeable odor. It has been found in a surprising manner that the anthraquinone derivatives characterized by the following formula in which n is a whole number between 2 and 6 inclusive, R represents a lower alkyl radical, NZ represents a heterocyclic radical such that the morpholine or piperidine residue and A is an anion, such as a halide or methylsulfate, do not possess this disadvantage. Since these compositions have moreover dyeing properties which are quite remarkable and yield shades that are resistant to sunlight, they are very advantageous for use in the cosmetic field. Since such compositions are generally used in the form of solutions for dyeing hair, it is very important, both for the persons whose hair is being dyed and for the personnel of the beauty salon, that the treatment takes place without releasing bad odors. The present invention, therefore envisages as a new article of manufacture the new chemical compositions of the above Formula 5.

Another object of the invention is to provide hair dyeing compositions characterized by the fact that they contain one or more compositions of the above general Formula 5.

Among the compositions which fall within the scope of the present invention the following are particularly advantageous: 1 methyl [I-anthraquinonylaminoethyl)- methylmorpholinium] sulfate and l-methyl [(L-anthraquinonylaminopropyl)-methyl-piperidine] sulfate.

The new compositions according to the invention are obtained from derivatives having a corresponding tertiary amine function.

17 The latter may be prepared from l-chloroanthraquinone by condensation using heat in the presence of mixture of copper acetate and potassium acetate with an alkaline diamine having the formula in which n and NZ have the same significance as in the general Formula 5, given above.

The quaternization of these tertiary anthraquinonic derivatives may be easily accomplished using a quaternizing agent such as methyl sulfate or an alkyl halide in the presence of an appropriate salt.

The dyeing solutions according to the invention are prepared by simply dissolving in water one or more compositions having the general Formula given above in the presence or in the absence of other coloring agents and by then introducing into the solution conventional ingredients such as dispersing agents, emollients, perfume, etc.

The concentration of the dyes may be varied within broad limits and their choice is a function of the result sought. The hair is colored by means of the solutions according to the invention in the usual manner by applying it preferably at room temperature to the hair for the length of time required.

The pH of the solution used may vary within broad limits and is preferably between 4.5 and 9.5.

The dyes according to the invention generally yield reddish colors.

The invention may be better understood with reference to the following examples:

PREPARATION OF COMPOSITIONS Example MIL-Preparation of methyl-[(l-anthraquinonylaminoethyl)-methyl-morpholinium] sulfate CH -CH 0 NH-CHr-CHg-N CH3 8040K.-

The 1(fl-morpholino-ethyl) amino anthraquinone is prepared by heating to reflux for 7 hours under agitation a mixture of 0.2 mole of l-chloro-anthraquinone and 0.8 mole of fl-amino-ethylmorpholine in solution with 240 cc. of isobutanol in the presence of 1.2 grams of potassium acetate and 0.1 gram of copper acetate.

This is dried, washed with water, dried at 100. The product is obtained with a yield of 55% and melts at l61-l62.

Analysis.--Calculated: C percent, 71.43; H percent, 5.95; N percent, 8.33. Found: C percent, 71.18; H percent, 6.02; N percent, 8.16.

Beginning with this base, the corresponding quaternary composition is prepared by treating it with methyl sulfate in toluene at 80.

The product is obtained with a yield of 94% and melts with decomposition at 214-217".

AnaZysis.--Calculated: N percent, 6.06. Found: N percent, 6.01.

Example LIV.Preparation of methyl-[(I-anthraquinonylaminopropyl)-methyl-piperidine] sulfate CHz-C H:

I-(y-piperidine-propyl)-amino-anthraquinone is prepared by earring to reflux at 7 hours a mixture of 0.05 mole of a-chloro-anthraquinone and 0.2 mol of v-aminopropyl-piperidine and 60 cc. of toluene in the presence of 5 grams of potassium acetate and 0.3 gram of copper acetate.

This is extracted with HCl, precipitated with NaOH and then dried and washed. The raw product is recrystallized in hexane and melts at 97-98 and is obtained with a yield of 58%.

Analysis.-Calculated: C percent, 75.86; H percent, 6.90; N percent, 8.04. Found: C percent, 75.81; H percent, 6.90; N percent, 8.13.

In order to obtain the quaternary this base is reacted with cold methyl sulfate in toluene in the customary manner.

The product obtained with a yield of 97% melts with decomposition at 162163.

Analysis-Calculated: N percent, 5.91. Found: N percent, 5.73-5.78.

APPLICATION OF THE COMPOSITION Example LV The following mixture is prepared:

Methyl-[ (I-anthraquinonylamino ethyl) -methyl-morpholinium] sulfate-1 gr.

Sodium carbonate q.s.p. pH 9 Water q.s.p. 100

This solution is applied to chestnut colored hair. It is left in contact for 15 minutes at room temperature. The hair is abundantly rinsed with water and dried. This yields a color having mahogany glints.

Example LVI The following mixture is prepared:

Methyl-[ (Lanthraquinonylaminopropyl) -methyl-piperidine] sulfate3 gr.

Octyl phenol condensed with 10 to 11 molecules ethylene oxide-2.5 gr.

Sodium carbonate q.s.p. pH 7 This solution is applied to white hair under the same conditions as in the preceding example and leads to a deep red color. 7

What is claimed is:

1. A process for dyeing live human hair which comprises applying thereto a compound selected from the group consisting of a dyestulf of the formula:

X o NH-Z l H I I X X and the quaternary ammonium salts of said dyestufi, in which one X is a -NHZ and the other two are hydrogen and in which NHZ is selected from the group consisting of NN dimethyl paraphenylene diamine and 4. The process of claim 1 in which n1 is an integer of 2, 3 or 6 and R and R together with the adjacent nitrogen is morpholino.

5. The process of claim 1 in which NH-Z is NN dimethyl paraphenylene diamine.

6. The process of claim 1 in which the dyestufi is a quaternary ammonium salt selected from the group consisting of bis(methyl methosulphate) and bis(benzyl chloride).

7. The process of claim 1 in which said dyestulfs are applied to the hair in an aqueous medium having a pH between 3 and 10.

8. The process of claim 7 in which said medium has a pH between 4.5 and 9.5.

9. A composition for dyeing live human hair comprising a compound selected from the group consisting of a dyestutr' of the formula:

2 h) NH-Z I I! X.

and the quaternary ammonium salts of said dyestutf, in which one X is a --NH-Z and the other two are hydrogen and in which NH--Z is selected from the group consisting of NN dimethyl paraphenylene diamine and in which R and R are selected from the group consisting of lower alkyl or together with the adjacent nitrogen morpholine or piperidine; and n is an integer from 2 to 6, in an aqueous solution having a pH between 3 and 10.

10. The composition of claim 9 having a pH between 4.5 and 9.5.

11. The composition as claimed in claim 9 which also contains a wetting agent.

12. The composition of claim 9 in which the dyestutf is one in which R and R, together with the adjacent nitrogen is morpholino and in which n is an integer of from 2 to 3.

13. The composition of claim 9 in which R and R together with the adjacent nitrogen is piperidino and in which n is an integer of from 2 to 3.

14. A composition for dyeing live human hair which comprises an aqueous solution having a pH of 3 to 9 and a compound selected from the group consisting of the dyestutf of the formula:

R! Y o and the acid addition and quaternary addition salts of said dyestufi in which n is an integer from 2 to 6 and in which the group is selected from the group consisting of lower dialkyl amine, morpholino and piperidino.

15. The composition of claim 14 wherein said dyestufi is the quaternary ammonium salt of Z-(B-diethylaminoethylamino)anthraquinone.

16. The composition of claim 14 wherein said dyestuff is 2-('y-diethylaminopropylamino)anthraquinone.

17. The composition of claim 14 wherein said dyestufi is Z-(fi-morpholinoethylamino) anthraquinone.

18. A process for dyeing live human hair which comprises applying thereto dyeing amounts of the quaternary ammonium salt of a dyestufi of the formula:

in which n is an integer from 2 to 6 inclusive, R is lower alkyl, NZ is selected from the group consisting of morpholino and piperidino, and A is selected from the group consisting of halogen and methylsulphate.

19. The process of claim 18 for dyeing live human hair wherein said salt is methyl-[(l-anthraquinonylaminoethyl) -methyl-morpholinium] sulfate.

20. The process of claim 18 for dyeing live human hair wherein said salt is methyl-[(l-anthraquinonylaminopro pyl -methyl-piperidine] sulfate.

21. A dyeing composition comprising an aqueous solution containing dyeing amounts of the quarternary ammonium salt of a dyestuff of the formula in which n is an integer from 2 to 6 inclusive, R is lower alkyl, and NZ is selected from the group consisting of morpholino and piperidino and A is selected from the group consisting of halogen and methylsulfate having a pH of 4.5 to 9.5.

22. The composition of claim 21, wherein said salt is methyl [(1 anthraquinonylaminoethyl) methyl-morpholinium].

' 23. The composition of claim 21, wherein said salt is methyl [(1 anthraquinonylaminopropyl) methylpiperidino].

References Cited UNITED STATES PATENTS 1,856,802 5/1932 Balley et a1 260378 XR 2,153,012 4/ 1939 Tatum 260378 XR 2,311,065 2/1943 McNally et al. 260-378 XR 3,040,064 6/1962 Grossmann 260380 3,153,059 10/1964 Straley et al 260-379 3,232,934 2/1966 Hoarse 260-378 XR 3,100,739 8/1963 Kaiser et a1. 16788 3,123,605 3/1964 Turetzky et a1 260247.5

ALBERT T. MEYERS, Primary Examiner VERA C. CLARKE, Assistant Examiner U.S. Cl. X.R. 

